Polyacrylate plastic compositions containing flame retardants

ABSTRACT

WHEREIN Z is bromine or chlorine, m and m&#39;&#39; are integers having a value of 1-5, i and i&#39;&#39; are integers having a value of 0-2, R is herein defined, M and M&#39;&#39; are each independent and are from the group oxygen, nitrogen or sulfur with the proviso that M and M&#39;&#39; cannot concurrently be oxygen in both cases, and A is chlorine, cyano, nitro, lower alkoxy, lower alkyl, fluorine, dialkylamino, phenyl, halo-phenyl, benzyl, or halo- benzyl.   Plastic compositions containing polyacrylates and halogenated aryl compounds having the formula:

United States Patent Anderson 1*Feb. 11, 1975 POLYACRYLATE PLASTIC [56] References Cited COMPOSITIONS CONTAINING FLAME UNITED STATES PATENTS RETARDANTS 3,385,8l9 5/l968 Gouinlock 260/4575 R 2 d M h. 3,560,441 2/1971 Schwarcz et 31.... 260/457 R [75 Inventor Arnold L n m 3,658,634 4/1972 Yanagi et al 161/403 [73] Assignee: Michigan Chemical Corporation, St. 3,717,609 2/1973 Kutner 260/4595 G L ,M' h. ouls Primary Examiner-M. J. Welsh l Notlcei The Porhoh of the term of this Attorney, Agent, or Firm--.lames .I Mullen; Robert M.

patent subsequent to July 16, 199i, Phi Robert s Frieman has been disclaimed. 22 Filed: Feb. 8, 1973 3 ABSTRACT astic compositions containing polyacrylates and hal PP 330,774 logenated aryl compounds having the formula:

I Z M R M Z l Related US. Application Data wherein Z is bromine or chlorine, m and in are inte- [63] Continuation-impart of Ser. N0. 260,240, June 6, g having a value of n are integers having 1972, abandoned. a value of 0-2, R is herein defined, M and M are each independent and are from the group oxygen, nitrogen [52] US. Cl 260/459 R, 260/42, 260/4222, 0r sulfur with the proviso that M and M cannot con- 260/45.75 R, 260/457 S currently be oxygen in both cases, and A is chlorine, [51] Int. Cl. C08f 45/60 cyano, nitro, lower alkoxy, lower alkyl, fluorine, dial- [58] Field of Search. 260/4595 G, 25 AJ, 45.95 C, kylamin ph nyl, -p ny benzyl, or halo 260/613 B, 33.2 R, 45.9 R, DIG. 24, 45.7 S; lO6/l5 FP zyl.

29 Claims, No Drawings POLYACRYLATE PLASTIC COMPOSITIONS CONTAINING FLAME RETARDANTS This application is a continuation-in-part of copending application Ser. No. 260,240, filed June 6, 1972 and now abandoned. The entire specification of this case, Ser. No. 260,240, is to be considered as incorporated herein by reference.

The prior art considered in conjunction with the preparation of this application is as follows: U.S. Pat. No. 2,130,990; U.S. Pat. No. 2,186,367; U.S. Pat. No. 2,329,033; U.S. Pat. No. 3,666,692; U.S. Pat. No. 3,686,320; U.S. Pat. No. 3,658,634; German Pat. No. l,l39,636; German Pat. No. 2,054,522; Japanese Pat.

No. (72) l4,500 as cited in Volume 77, Chemical Abstracts, column l53737k (1972); Chemical Abstracts, Volume 13, column 448 Chemical Abstracts, Volume 31, column 7045 and Journal of the Chemical Society, pages 2972-2976 (1963). All ofthese publications are to be considered as incorporated herein by reference.

The present invention relates to plastic compositions containing polyacrylates. More specifically, the present invention covers plastic compositions containing polyacrylates and certain halogenated aryl compounds (hereinafter defined) as flame retardants for said plastic compositions.

Polyacrylates and utility thereof are known in the art as exemplified by Acrylic Resins, M. B. Horn, (Reinhold Plastics Applications Series), Reinhold Publishing Corporation, New York, 1960 and Encyclopedia of Polymer Science and Technology, Vol. 1, pages 246-328, John Wiley & Sons, lnc., New York 1964 and which publications are in toto incorporated herein by reference.

The need for flame retarding polyacrylates has also been recognized in the art as exemplified by the two above-described publications and by U.S. Pat. No. 3,422,048 which is incorporated herein by reference.

The resultant disadvantages in the utilization of various prior art materials as flame retardants for polyacrylates include, without limitation, factors such as thermal migration. heat instability, light instability, non'biodegradable, toxicity, discoloration and the large amounts employed in order to be effective. Thus, there is always a demand fora material which will function as a flame retardant in polyacrylates and concurrently will not, by incorporation therein, adversely effect the chemical and/or physical and/or mechanical properties of the resultant composition.

The prior art problem of providing a flame retarded polyacrylate composition having desired chemical, physical and mechanical properties has now been substantially solved by the present invention and the ahovcdeseribed disadvantages substantially overcome.

Accordingly. one of the main objects of the present invention is to provide polyacrylate compositions which are flame retarded.

Another object of the present invention is to provide a material for polyacrylate compositions which will not substantially adversely effect the chemical and/or physical and/or mechanical properties of said compositions.

A further object of the present invention is to provide a flame retardant which is economic and easy to incorporate into polyacrylate without being degraded or decomposed as a result of blending or processing operatrons.

It has been found that the foregoing objects can be obtained by the incorporation of a new class of halogenated aryl compounds in polyacrylate to subsequently provide flame retarded compositions which exhibit outstanding chemical, physical and mechanical properties.

The halogenated aryl compounds used in the present invention compositions have the formula:

ln Formula I above, Z is bromine or chlorine, m and In are integers each independently having a value of l-S; i and i are integers each independently having a value of 0-2; M and M are each independent and are from the group oxygen, nitrogen and sulfur with the proviso that M and M cannot concurrently be oxygen in both cases and where M and/or M is nitrogen, the formula is where X H, Cl, Br

(h) n c 6} ca where S saturated ring CH CH In Formula I, i m or i m is not greater than 5. polymeric systems tomake the resultant polymer flame It is to be understood that all of the compounds fallre n ing within the above Formula I and as heretofore de- Illustrative ut on) of So e Of the fined are generically described herein'as halogenated present invention halogenated aryl compounds are aryl compounds. 5 shown below:

(1) A A r Z M' R I M Z c The halogenated aryl compounds are found to be the exemplary definitions of A, Z, M. M, R, m. m, i compatible with and effective additives for various and i are listed in Table l.

12211. Compound No z m m' A i i R M M 1 B 1 1 0 0 11 s s 2 Br 1 3 o o c u s a 3 Br 2 2' c1 1 1 e n q if Br 2 I 2 -cN 1 1 c 11 1; ll 5 Br 2 2 -N0 1 1 0 11 I o .N r I 6 c1 2 2 -ocn 1 1 c 11 5 s 7 Br 3 3 -ocu 1 1 c 3 I s o 3 Br 2 2 -cn 1 1 c 11 N 1 N 9 Br 2 2 F 1 1- 0 3 I s s 10 Br 2 2 -N(C1i 1 1 0 1 p" i N i N 11 I Br 2 2 4 11 1 1. c A I N 1 s 12 c1 2 2 -c H Br 1 r 1 c 11 I i N s 13 Br 2 2 -CH2C,5H5 1 1 0 11 Y s s 14 Br 2 2 -CH2C6H3B2:2 1 1 c 11 N N 1s c1 3 I 3 -'c B c1 1 1 c 11 N N 16 Br 3 3 F l 1 b 13 v N 0 17 Br 2 1 -l(CH 1 0 C336 N i s 4 1:; Br 2 3 -N(CH3) 2 1 0 0 11 I N o 19 c1 3 3 -C H Br 1 1 0 11 i s s 20 i Br 3 3 01 I 2 2 c 11 s N 21 Br 2 2 c1 1 1 CIi(Cl-l )CH N N 22 Br 4 4 c1 1 1 CH(CH )Cl-l CH SV 0 23 Br v 3 3 F 2 2 CH2CH(CH3)CH2CH2 o N 2 I B 1 1 r 42,11 I I 1 1 c11 N: N 25 B1: 1 1 -oc a 1 1 c 11 v Q N Q Table I {Con' (D Compound No. 2 m m A 1'. 1' R M 212 B1: 2 2 2 :1 a 1 1 11 6 021 n N 213 Br 2 2 --ca c n 1 1 N s 214 B1: 2 2 -CH C H Br 1 1 i z N 215 Br 3 3 4 11 01 1 1 Z s s 216 01 3 3 r 1 1 C--@ N 217 c1 2 2 -ca- 2 2 1:

2113 Br 4 4 o 0 32 a s 219 C1 3 3 C H Br J l H C CH O N 220 C1 3 3 -N0 2 2 H C-@ g'g S S 221 01 2 2 -0ca 1 1 CH2 s n 222 e1 4 4 411 1 1 Q N u 223 01 3 3 1 2 2 112C 0' Is a 224 B1- 1 -C 'H 1 1 5 N 0 22s Br 1 1 -0011 11 1 419 2 T 2 N N In general, the halogenated aryl compounds are presuch as distillation or crystallization. Where the end pared by reacting a halogenated phenol, thiophenol or product requires recovery via crystallization, various aryl amine with a halogenated alkane at elevated temaromatic solvents such as benzene, toluene, xylene, diperatures in the presence of a basic material such as alchlorobenzene and the like can be used.

kali metal hydroxides, carbonates, bicarbonates, oxides 40 Specifically, the symmetrical halogenated aryl comand hydrides. The preferred alkali metals are potassium pounds are prepared. for example, according to the foland sodium. Where one desires to increase, for examlowing reactionsz.

. base 2-2 $11 x-- R-X (III) A1 1! Z S R S 2 ple, ease of handling the reaction mass, solvents such I the bove reaction, X is halogen, preferably chlo- HS kfitones -gacetone, t y hyl ketone, and rine and R is the same as defined herein. Where m and m hyl i -h yl 310011018 et anol. eth- 6( m and i and i are different integers, then equivalent anol, iso-propyl alcohol, butyl alcohol and glycols), molar portions of the particular halogenated phenol, aqueous solvents (eg. water, a mixture of water and althiophenol or aryl amine are used with equivalent porcohol and a mixture of water and ketone), and polar tions of dissimilar halogenated phenol, thiophenol or aprotic solvents such as dimcthylformamide (DMF). aryl amin dimethyl sulfoxide (DMSO) and ethers such as tetrahy- 65 drofuran (THF), can be employed. The desired end The unsymmetrical halogenated aryl compounds are product the halogenated aryl compound, can be reprepared, for example, according to the following reaccovered from the reaction mass via various methods tions:

2. on x-Rxz 1n the above reaction, X and R are the same as mentioned above.

The above reactions are conducted at temperatures ranging from the freezing point of the initial reaction mass to the boiling point thereof. Preferably the temperatures are from about 40 C to about 200 C and more preferably from about 50 C to about 175 C. It is to be understood that the reaction can be conducted under sub-atmospheric (e.g. one-tenth-eight-tenths atmospheres), atmospheric or super-atmospheric (e.g. 1.5-10 atmospheres) pressure. Preferably, the reaction is carried out at atmospheric pressure.

The above described processes can be carried out with conventional, readily available chemical processing equipment. For example, a conventional glass-lined vessel provided with heat transfer means, a reflux condenser and a mechanical stirrer can be advantageously utilized in practicing any of the preferred embodiments of the invention described in the examples set forth herein. The above described processes and resultant products. i.e., the halogenated aryl compounds, are more fully described in the present applicants copending patent application Ser. No. 330,838 filed Feb. 8, 1973, and which is incorporated herein by reference.

The amount of halogenated aryl compound employed in the present invention compositions is any quantity which will effectively render the polyacrylate containing composition flame retardant. In general, the amount used is from about 1% to 25% by weight, based on the total weight of the composition. Preferably. the amount employed is from about 5% to about 20% by weight. It is to be understood that any amount can be used as long as it does not substantially adversely effect the chemical and/or physical and/or mechanical properties of the end polymer composition. The amount utilized, however, is such amount which achieves the objectives described herein.

It is to be understood that the terms polyacrylates as used herein means acrylic polymers including acrylic acid polymers and copolymers and acrylic ester polymers and copolymers. For example, there may be mentioned materials which contain one of the repeating units CQOR (Acrylate polymers) where R is an alkyl or aryl radical or (in water-soluble polymers) a monovalent cation.

Thus the polyacrylates used in the present invention compositions is any polyacrylates herein defined and which one so desires to flame retard. It is to be understood that the polyacrylates used can be a virgin material, i.e. substantially free of additives such as stabilizers, plasticizers, dyes, pigments, fillers, and the like, or the polyacrylates can have additives (such as those mentioned and described herein) already contained therein or added concurrently with or after the addition of the halogenated aryl compounds.

Another facet of the present invention relates to the use of certain metal compounds with the halogenated aryl compounds to promote a cooperative effect therebetween and thus enhance the flame retardancy of the resultant plastic composition as compared to the flame retardancy of either one component used separately. These enhancing agents are from the group antilmony, arsenic, bismuth, tin and zinc-containing com- :pounds. Without limitation, examples of said enhancing agents include Sb O SbCl SbBr Sbl SbOCl, A5 0 As O ZnBO BaB O 'H O, 2-ZnO-3B O -3.5- H 0 and stannous oxide hydrate. The preferred en- 5 hancing agent is antimony trioxide.

The amount of enhancing agent employed in the present invention compositions is any amount which when used with said halogenated aryl compounds will promote a cooperative effect therebetween. In general, the amount employed is from about 1% to about 15%, preferably from about 2% to about 10%, by weight, based on the total weight of plastic composition. Higher amounts can be used as long as the desired end result is achieved.

lt is also within the scope of the present invention to employ other materials in the present invention compositions where one so desires to achieve a particular end result. Such materials include, without limitation, adhesion promotors; antioxidants; antistatic agents; antimicrobials; colorants; flame retardants such as those listed on pages 456-458, Modern Plastics Encyclopedia, ibid, (in addition to the new class of flame retardants described herein); heat stabilizers; light stabilizcooa (Methacrylate polymers) ers; pigments; plasticizers; preservatives; ultraviolet stabilizers and fillers.

In this latter category, i.e. fillers, there can be mentioned without limitation, materials such as glass; carbon; cellulosic fillers (wood flour, cork and shell flour); calcium carbonate (chalk, limestone, and precipitated calcium carbonate); metal flakes; metallic oxides (aluminum, beryllium oxide and magnesia); metallic powders (aluminum, bronze, lead, stainless steel and zinc); polymers (comminuted polymers and elastomerplastic blends); silica products (diatomaceous earth, novaculite, quartz, sand, tripoli, fumed colloidal silica, silica aerogel, wet process silica); silicates (asbestos, kaolimite, mica, nepheline syenite, talc, wollastonite, aluminum silicate and calcium silicate); and inorganic compounds such as barium ferrite, barium sulfate, molybdenum disulfide and silicon carbide.

The above mentioned materials, including fillers, are more fully described in Modern Plastics Encyclopedia, ibid, and which publication is incorporated herein (in toto) by reference.

The amount of the above described materials employed in the present invention compositions can be any quantity which will not substantially adversely effeet the desired results derived from the present invention compositions. Thus, the amount used can be zero percent. based on the total weight of the composition, up to that percent at which the composition can still be classified as a plastic. In general, such amount will be from about to about 75% and specifically from about 1% to about 50%.

The halogenated aryl compounds can be incorporated in to the polyacrylates at any processing stage in order to prepare the present invention compositions. In general, this is undertaken prior to fabrication either by physical blending or during the process of forming polyacrylates per se. Where one so desires, the halogenated aryl compounds may be micronized into finely divided particles prior to incorporation into the polyacrylates.

EXAMPLE I A virgin polymethylmethacrylate plastic material, (Lucite-l 80, a product of E. l. duPont de Nemours and Company, Wilmington, Del. and being substantially free of additives) is utilized as the base resin in order to prepare 26 formulations (plastic compositions). With the exception of formulation No. I the particular halogenated aryl (and the antimony trioxide enhancing agent where indicated) is incorporated into the plastic by adding both to a Brabender mixer (Plastic- Corder, Torque Rheometer, Model PLV-ISO, C. W. Brabender Instruments lnc., South Hackensack, N..I.). The mixer is equipped with a pair of roller type blades positioned within a head provided with heat transfer means.

The resultant mixture is heated to about 300 C.; at this temperature, it is in a molten state. The percentages by weight of each component utilized in the respective formulations are listed in Table II. Each formulation is discharged from the mixer and upon cooling solidifies and is ground into chips. The chips are subjected to compression molding in a Wabash press by placing said chips between two platens, the bottom of which contains four equal size depressions 3 inches by 5 inches by /8 inch deep. The top platen is then placed over the bottom platen and heat transfer means supplied thereto in order to melt said chips and thus provide solid samples (after cooling) for testing.

Portions of the samples of each respective formulation (Nos. l-26) prepared according to the above described procedure are then subjected to two different standard flammability tests, i.e. UL 94 and ASTM D- 2863-70. The UL 94 is, in general, the application of a burner to a test specimen (strip) for a certain period of time and observation of combustion, burning, and extinguishment. This procedure is fully set forth in Underwriters Laboratories bulletin entitled UL 94, Standard for Safety, First Edition, September I972 and which is incorporated herein by reference. ASTM No. D-2863-7O is a flammability test which correlates the flammability of a plastic specimen to the available oxygen in its immediate environment; this correlation is stated as an Oxygen Index, 0.1., level predicated upon the percent oxygen in the gaseous medium which is required to just provide a steady state of continuous burning of the plastic specimen. This ASTM method is fully described in I971 Annual Book of ASTM Standards Part 27, published by the American Society For Testing and Materials, 1916 Race Street, Philadelphia, Pa.; this publication is to be considered as incorporated (in toto) herein by reference.

The results of these flammability tests are shown in Table II.

TABLE II FLAMMABILITY DATA FOR POLYACRYLATE PLASTIC COMPOSITIONS CONTAINING HALOGENATED ARYL COMPOUNDS FORMULA- HALOGEN ATED ARYL ENHANCING oxYGEN UL 94 TION COMPOUND AGENT INDEX 1. 0 0 20.0 $1; 2. 1 20 0 21.5 513 3. 1 20 10 26.0 sea 4. 2 20 0 24.0 513 5. 2 20 10 33.5 SE0 6. 3 2o 0 25.5 se 7. 3 20 10 36.0 SE-O s. 4 20 0 24.5 SB 9. 4 20 10 355 SEO 10. 32 20 0 26.0 SE62 11. 32 20 10 36.0 SE-() 12. 37 20 0 22.5 SB 13. 37 20 10 29.5 SE-() 14. 65 20 0 235 SB 15. 65 20 10 28.5 SE-] 16. 79 20 0 24.0 s13 17. 79 20 10 29.0 SE-() 18. 122 20 0 225 $13 19 122 20 10 2x0 SB-I TABLE I I Continued FLAMMABILITY DATA FOR POLYACRYLATE PLASTIC COMPOSITIONS CONTAINING HALOGENATED ARYL COMPOUNDS FORMULA- HALOGENATED ARYL ENHANCING OXYGEN UL 94 TION COMPOUND AGENT INDEX NO. NO. 7( Sb Q 7:

20. I43 20 O 245 SB 21. 143 20 10 36.5 SE-() 22. I59 20 O 22.5 SB 3. 159 2O 10 29.0 SE-O 24. 181 20 21.0 SB 25. 181 20 28.0 SE-l 26. 205 2O 10 35.5 SE-O Referring to Table II, the halogenated aryl number relates to the structural formulae heretofor set forth in Table I; a difference of 2% in the Oxygen Index values is considered significant; and the UL 94 values are on a graduated scale wherein the highest degree to lowest degree of flame retardancy is respectively SE-O, SE-l, SE-Z, SB and Burns.

The results shown in Table II demonstrate the unique effectiveness of these halogenated aryl as flame retardants for polyacrylates. Specifically, formulation No. 1 (the control) had a 0.1. of 20.0 and UL 94 value of SB. In the even numbered formulations, the use of the particular halogenated aryl results in a significant increase in fire retardancy as measured by O.I. (While these formulations also had a SB rating, UL 94, the individual 'U.L. rating has a wide range of values and thus the 0.1.

EXAMPLE II Example I is repeated twice; once using a 10% halogenated aryl compound level and 3% Sb O level and secondly, and 5% levels respectively. At both levels, the 01. values and UL 94 ratings are slightly lower than the level of Example I.

EXAMPLE III Portions of the solid samples of Formulation Nos. l-26 prepared according to the above described procedure of Example I are subjected to the following ASTM tests in order to ascertain other properties of the resultant plastic composition:

1 l Tensile Strength (at break) (2) Flcxural Strength (3) Flexurul Modulus (4) Notched Izod Impact (5) Heat Distortion Temperature (HDT) ASTM Test No. D638-61T;

: ASTM Test No. D79tl-63;

: ASTM Test No. D790-63;

: ASTM Test No. D256-56; and

1 ASTM Test No. D648-56.

Each of the aforementioned ASTM Tests arestandard tests in the art and are utilized collectively in order to ascertain the efficacy of a polymeric system as an overall flame retarded composition for commercial application. All of these ASTM Tests are to be considered as incorporated herein by reference.

The results of these ASTM tests show that the physical properties of the present invention compositions are basically the same (except 0.1. and UL 94 values) as the plastic material without the flame retardant (i.c. formulation No. 1). Thus, there is no substantial adverse effect on the physical properties of the plastic material when the novel compounds are incorporated therein.

EXAMPLE IV The procedure of Examples I, II and III are repeated except that the enhancing agent used is zinc borate instead of Sb O Substantially the same results are obtained using zinc borate as those obtained using Sb. ,O,,.

EXAMPLE V Strip samples of each of Formulation Nos. 1 through 26 Table II, are subjected to light stability tests via the use of a Weather-Ometer, model 25/18 W.R., Atlas Electrical Devices Company, Chicago, Ill. Utilizing an operating temperature of F and a 50% relative humidity, each strip is subjected to 200 hours of simulated daylight via the use of a carbon arc. The results show that after 200 hours, there is no significant discoloration in any strip tested and which demonstrates that the present invention compositions are highly resistant to deterioration by light.

EXAMPLE VI Samples of each of Formulation Nos. 1 through 26 Table II, are subjected to temperature (thermal) stability tests via the use of thermal gravimetric analysis (TGA). This test employed the use of a Thermal Balance", model TGS-l, Perkin-Elmer Corporation, Norwalk, Conn. and an electrical balance, Cahn 2580 model, Cahn Instrument Company, Paramount, Calif. The results of these tests show that the halogenated aryl compound containing Formulations had more than adequate stability for melt processing and subsequent heat aging (i.e. high temperature applications) and thus demonstrating that the particular halogenated aryl are quite compatible with the plastic material. The halogenated aryl compound stability thus aids in providing sufficient flame retardancy at the plastic decomposition temperature. This test also demonstrates that these compounds do not exhibit migration.

In view of the foregoing Examples and remarks, it is seen that the plastic compositions, which incorporate these compounds, possess characteristics which have been unobtainable in the prior art. Thus, the use of these compounds in the above described plastic material as flame retardants therefor is quite unique since it is not possible to predict the effectiveness and functionality of any particular material in any polymer system until it is actively undergone incorporation therein and the resultant plastic composition tested according to various ASTM Standards. Furthermore, it is necessary, in order to have commercial utility, that the resultant flame retarded plastic composition possess characteristics such as being non-toxic. Use of these compounds in the plastic material has accomplished all of these objectives.

The above examples have been described in the foregoing specification for the purpose of illustration and not limitation. Many other modifications and ramifications will naturally suggest themselves to those skilled in the art based on this disclosure. These are intended to be comprehended as within the scope of this invention.

What is claimed is:

l. A plastic composition containing polyacrylate having incorporated therein a flame retardant which is a halogenated aryl compound having the formula:

wherein Z is selected from the group consisting of bromine or chlorine; m and m are integers having a value of 1-5; i and i are integers having a value of 0-2; A is selected from the group consisting of chlorine, cyano, nitro, lower alkoxy, lower alkyl, fluorine, dialkylamino, phenyl, halo-phenyl, benzyl, or halobenzyl; and R is wherein iis selected from the group consisting of bromine or chlorine; m and m are integers having a value of 1-5; i and are integers having a value of0-2; M and M are each independent and are selected from the group consisting of oxygen, nitrogen or sulfur with the proviso that M and M cannot concurrently be oxygen in both cases and where M and/or M is nitrogen, the formula is A is selected from the group consisting of chlorine,

cyano, nitro, lower alkoxy, lower alkyl, fluorine, dialkylamino, phenyl, halo-phenyl, benzyl, or halobenzyl; and R is selected from the group consisting of selected from the group consisting of a. alkylene group having from one to six carbon cs CH where x 11,01, Br-

a. alkylene group having from one to six carbon CH2 C(O) CH2 atoms b. CH -CH(OH)-CH c. CH CH(CH OH)CH (3) CH ---ca 2)u' 2)uwhere w l-6 where X H cl g where S saturated a. m It ring CH2C(O) CH2 6. The composition as set forth in claim 5 wherein i CH and i are both 0.

2 7. The composition as set forth in claim 5 wherein i and i are both I.

8. The composition as set forth in claim 5 wherein i and i are both 2. ,5 9. The composition as set forth in claim 6 wherein R where S saturated ring is an alkylene group having from l to 6 carbon atoms.

10. A plastic composition containing polyacrylate having incorporated therein a flame retardant which is i a halogenated aryl compound having the formula:

wherein Z is selected from the group consisting of bromine or chlorine; m and m are integers having a value of l-; i and i are integers having a value of 0-2; A is selected from the group consisting of chlorine, cyano, nitro, lower alkoxy, lower alkyl, fluorine, dialkylamino, phenyl, halo-phenyl, benzyl, or halobenzyl; and R is selected from the group consisting of a. alkylene group having from one to six carbon atoms b. CH CH(OH)CH d. (CH .O(CH where w 1-6 ere X H, 01-, B2

f. CH C(O)CH (a) c11 ca where S n saturated ring 11. The composition as set forth in claim wherein [and i are both 0.

12. The composition as set forth in claim 10 wherein iand i are both 1.

13. The composition as set forth in claim 10 wherein [and i are both 2.

14. The composition as set forth in claim 11 wherein R is an alkylene group having from I to 6 carbon atoms.

15. A plastic composition containing polyacrylate having incorporated therein a flame retardant which is i a halogenated aryl compound having the formula:

wherein Z is bromine or chlorine, m and m are integers having a value of l5, i and 1" are integers having a value of 0-2; A is chlorine, cyano, nitro, lower alkoxy, lower alkyl, fluorine, dialkylamino, phenyl, halophenyl, benzyl, or halobenzyl; and R is selected from the group consisting of a. alkylene group having from one to six carbon atoms c. CH -CH(CH OH)-CH where x a, ct; Br

f. ca. -c o) ca (5) ca ca where S saturated ring wherein Z is bromine or chlorine, m and m are integers having a value of l5; iand i are integers having a value of 02; A is chlorine, cyano, nitro, lower alkoxy, lower alkyl, fluorine, dialkylamino, phenyl, halophenyl, bcnzyl, or halobenzyl; and R is selected from the group consisting of a. alkylcnc group having from one to six carbon atoms 011 'cit wheire x 11, 01, B1:

in n 6 1 f. CH -C(O)CH where S saturated ring wherein Z is bromine or chlorine, m and m are integers having a value of 1-5; 1' and i are integers having a value of 0-2; A is chlorine, cyano, nitro, lower alkoxy, lower alkyl, fluorine, dialkylamino, phenyl, halophenyl, benzyl, or halobenzyl; and R is selected from the group consisting of a. alkylene group having from one to six carbon atoms 5 b. CH CH(OH)-CH c. CH CH(CH OH)CH 2)u' 2)u where w l 6 (e) n l0 V I cs c11 where X H, I1, 3

f. CH C(O)-CH (g) 011 ca where S saturated ring 26. The composition as set forth in claim 25 wherein iand i are both 0.

27. The composition as set forth in claim 25 wherein iand i are both 1.

28. The composition as set forth in claim 25 wherein [and i' are both 2.

29. The composition as set forth in claim 26 wherein R is an alkylene group having from 1 to 6 carbon atoms.

UNITE STATES PATENT OFFICE EETTTCATE OE EQRECTTON PATENT NO. 1 3,865,782

DATED February 11, 1975 INVENTOR(S) Arnold L, Anderson It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 25, line 31 (being the first line after the first structural formula of Claim 1) after wherein: delete "i" and substitute therefor gn'ncd an fiealed this of August 1975 {SEAL} Arrest: 

1. A PLASTIC COMPOSITION CONTAINING POLYACRYLATE HAVING INCORPORATED THEREIN A FLAME RETARDANT WHICH IS A HALOGENATED ARYL COMPOUND HAVING THE FORMULA:
 2. The composition as set forth in claim 1 wherein i and i'' are both
 0. 3. The composition as set forth in claim 1 wherein i and i'' are both
 1. 4. The composition as set forth in claim 1 wherein i and i'' are both
 2. 5. A plastic composition containing polyacrylate having incorporated therein a flame retardant which is a halogenated aryl compound having the formula:
 6. The composition as set forth in claim 5 wherein i and i'' are both
 0. 7. The composition as set forth in claim 5 wherein i and i'' are both
 1. 8. The composition as set forth in claim 5 wherein i and i'' are both
 2. 9. The composition as set forth in claim 6 wherein R is an alkylene group having from 1 to 6 carbon atoms.
 10. A plastic composition containing polyacrylate having incorporated therein a flame retardant which is a halogenated aryl compound having the formula:
 11. The composition as set forth in claim 10 wherein i and i'' are both
 0. 12. The composition as set forth in claim 10 wherein i and i'' are both
 1. 13. The composition as set forth in claim 10 wherein i and i'' are both
 2. 14. The composition as set forth in claim 11 wherein R is an alkylene group having from 1 to 6 carbon atoms.
 15. A plastic composition containing polyacrylate having incorporated therein a flame retardant which is a halogenated aryl compound having the formula:
 16. The composition as set forth in claim 15 wherein i and i'' are both
 0. 17. The composition as set forth in claim 15 wherein i and i'' are both
 1. 18. The composition as set forth in claim 15 wherein i and i'' are both
 2. 19. The composition as set forth in claim 16 wherein R is an alkylene group having from 1 to 6 carbon atoms.
 20. A plastic composition containing polyacrylate having incorporated therein a flame retardant which is a halogenated aryl compound having the formula:
 21. The composition as set forth in claim 20 wherein i and i'' are both
 0. 22. The composition asa set forth in claim 20 wherein i and i'' are both
 1. 23. The composition as set forth in claim 20 wherein i and i'' are both
 2. 24. The composition as set forth in claim 21 wherein R is an alkylene group having from 1 to 6 carbon atoms.
 25. A plastic composition containing polyacrylate having incorporated therein a flame retardant which is a halogenated aryl compound having the formula:
 26. The composition as set forth in claim 25 wherein i and i'' are both
 0. 27. The composition as set forth in claim 25 wherein i and i'' are both
 1. 28. The composition as set forth in claim 25 wherein i and i'' are both
 2. 29. The composition as set forth in claim 26 wherein R is an alkylene group having from 1 to 6 carbon atoms. 